CN103890092B - There is good shock strength, mobility and chemical-resistant fire retardation PC/ABS composition - Google Patents

There is good shock strength, mobility and chemical-resistant fire retardation PC/ABS composition Download PDF

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CN103890092B
CN103890092B CN201280053670.9A CN201280053670A CN103890092B CN 103890092 B CN103890092 B CN 103890092B CN 201280053670 A CN201280053670 A CN 201280053670A CN 103890092 B CN103890092 B CN 103890092B
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weight part
moulding compound
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CN103890092A (en
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V.塔施纳
T.埃克尔
D.维特曼
P.克卢帕蒂农
P.普里斯特
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Covestro Deutschland AG
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Bayer Pharma AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The present invention relates to flame retardant molding composition, it is by polycarbonate, graftomer and do not form containing the anhydride modified a-alkene terpolymer of rubber, described composition not only has good flow behavior under 1.5mm and UL94V-0 grade, and has good (breach) shock strength and high chemical resistant properties.These moulding compounds are particularly suitable for the thin-walled casing component in Electrical and Electronic field.

Description

There is good shock strength, mobility and chemical-resistant fire retardation PC/ABS composition
The present invention relates to the resistivity against fire moulding compound comprising polycarbonate and graftomer, described composition also demonstrates good (breach) shock strength and height chemical resistant properties under 1.5mm and UL94V-0 grade except good flowing property.These moulding compounds are particularly suitable for the thin-walled casing component in Electrical and Electronic field.
The fire resistance polycarbonate composition of the shock strength with improvement is described in US5120778, described composition comprises the olefinic rubber of polycarbonate resin, halogenation phthalic imidine and the halogenation oligo-ester carbonate as fire retardant, PTFE (tetrafluoroethylene) as anti-dripping agent and graft modification, and the olefinic rubber of described graft modification is one or more unsaturated dicarboxylic acids or the graftomer of its acid anhydrides on ethylenic copolymer grafting basis.
The painted non-flame resistant plasticity PC/ABS hot in nature moulding compound with the ethylenic copolymer of 1-9% grafting is known by EP494602A2, and the ethylenic copolymer of described grafting is the graftomer of acid anhydrides on the skeleton of ethylenic copolymer of one or more undersaturated dicarboxylic acid or described acid.
In US5087524, describe the thermoplastic resin composition of the properties-correcting agent containing acid anhydrides comprising aromatic polycarbonate and 0.5-5%, but do not disclose the concrete olefinic terpolymer containing acid anhydrides and according to composition of the present invention.
Application JP2001294742A, JP08188708A, JP3212468B2 and JP63156850 describe the non-flame resistant polycarbonate compositions comprising ethylene-propylene-copolymer-maleic anhydride.
Therefore the object of this invention is to provide polycarbonate molding compositions, described composition has good notched Izod impact strength, mobility and chemical resistant properties and good flame retardant resistance.
Surprisingly, find now: if use ethylene-propylene-octene-copolymer-maleic anhydride in flame retardant resistance PC/ABS blend, then obtain above-mentioned performance.
The feature that the moulding compound of formation like this is given prominence to is the mechanical property improved, and as high notched Izod impact strength and good mobility and high chemical resistant properties, and does not demonstrate any negative impact to flame retardant resistance.
The invention provides fire-resistant thermoplastic composition, it comprises:
A) 50.0-90.0 weight part, preferred 52.0-80.0 weight part, particularly preferably at least one aromatic polycarbonate of 54.0-75.0 weight part,
B) 4.0-14.0 weight part, preferred 5.0-12.0 weight part, particularly preferably at least one graftomer of 7.0-11.0 weight part,
C) 0.0-15.0 weight part, preferred 1.0-10.0 weight part, particularly preferably vinyl (being total to) polymkeric substance of 2.0-8.0 weight part,
D) 1.0 – 20.0 weight parts, preferably 5.0 – 18.0 weight parts, more preferably 6.0 – 16.0 weight parts, particularly preferably at least one phosphonium flame retardant of 9.0 – 15.0 weight parts,
E) 0.5 – 5.0 weight part, preferably 0.75 – 3.5 weight part, more preferably 0.5 – 2.5 weight part, particularly preferably at least one of 1.0 – 2.0 weight parts is not containing the anhydride modified a-alkene terpolymer of rubber,
F) 0.0-25.0 weight part, preferred 5.0-20.0 weight part, particularly preferably at least one filler of 12.0-18.0 weight part,
G) 0-10.0 weight part, preferred 0.5-8.0 weight part, particularly preferably other conventional additives of 1.0-6.0 weight part,
Wherein component A)-F) weight part sum add up to 100 weight parts.
Particularly preferred moulding compound also comprises 0.05-5.0 weight part except other optional additive, preferred 0.1-2.0 weight part, and particularly preferably the fluorinated polyolefin of 0.3-1.0 weight part is as component G).
Particularly preferred moulding compound also comprises 0.1-1.5 weight part except other optional additive, preferred 0.2-1.0 weight part, particularly preferably the releasing agent of 0.3-0.8 weight part such as pentaerythritol tetrastearate as component G).
Particularly preferred moulding compound also comprises 0.01-0.4 weight part except other optional additive, preferred 0.03-0.3 weight part, particularly preferably at least one stablizer of 0.06-0.2 weight part is as component G), described stablizer is such as selected from sterically hindered phenol, phosphorous acid ester and their mixture and is particularly preferably Irganox B900.
In addition, particularly preferably the combination of above-mentioned three kinds of additive PTFE, pentaerythritol tetrastearate and IrganoxB900 as component G).
component A
The aromatic polycarbonate according to component A be applicable to according to the present invention and/or aromatic polyestercarbonates are known by document or prepare (for the preparation of aromatic polycarbonate by the method known by document, see such as Schnell, " ChemistryandPhysicsofPolycarbonates ", IntersciencePublishers, 1964 and DE-AS1495626, DE-A2232877, DE-A2703376, DE-A2714544, DE-A3000610, DE-A3832396; Such as, for the preparation of aromatic polyestercarbonates, DE-A3077934).
Such as by phase interface method, optional usage chain terminator, such as single phenol and the optional branching agent using trifunctional or be greater than trifunctional, such as triphenol or four phenol, by making diphenol and carbonyl halide, preferred phosgene, and/or with aromatics dicarboxylic acid dihalide, preferred benzene dicarboxylic acid dihalide carries out reaction to prepare aromatic polycarbonate.Also can be prepared by melt polymerization method by diphenol and such as diphenyl carbonate reaction.
Diphenol for the preparation of aromatic polycarbonate and/or aromatic polyestercarbonates is preferably those of formula (I)
Wherein: A is singly-bound, C 1-C 5-alkylene base, C 2-C 5-alkylidene, C 5-C 6-ring alkylidene ,-O-,-SO-,-CO-,-S-,-SO 2-, C 6-C 12-arylidene, this arylidene can condense optionally containing other aromatic ring heteroatomic,
Or the group of formula (II) or (III)
B is respectively C 1-C 12-alkyl, preferable methyl, halogen, preferred chlorine and/or bromine,
X is 0,1 or 2 separately independently of each other,
P is 1 or 0, and
R 5and R 6for each X 1be can select separately and independently of each other for hydrogen or C 1-C 6-alkyl, preferred hydrogen, methyl or ethyl,
X1 is carbon, and
M represents the integer of 4-7, preferably 4 or 5, and condition is at least one atom X 1upper R 5and R 6it is alkyl simultaneously.
Preferred diphenol is quinhydrones, Resorcinol, dihydroxydiphenol, two (hydroxyphenyl)-C 1-C 5-alkane, two (hydroxyphenyl)-C 5-C 6-cycloalkanes, two (hydroxyphenyl) ether, two (hydroxyphenyl) sulfoxide, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfone and α, α-bis-(hydroxyphenyl)-diisopropyl benzene and their ring brominated and/or the derivative of ring chlorinated.
Particularly preferred diphenol is 4,4'-dihydroxybiphenyl, bisphenol-A, 2, two (4-the hydroxyphenyl)-2-methylbutane, 1 of 4-, 1-pair-(4-hydroxyphenyl)-hexanaphthene, 1,1-pair-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, 4,4'-dihydroxydiphenyl thioether, 4,4'-dihydroxy-diphenyl sulfones and their two and tetrabormated or two (the chloro-4-hydroxyphenyl of the 3-)-propane, 2 of chlorinated derivatives such as 2,2-, 2-two-(3,5-bis-chloro-4-hydroxyphenyl)-propane or 2,2-be two-(the bromo-4-hydroxyphenyl of 3,5-bis-)-propane.2,2-is two-and (4-hydroxyphenyl)-propane (dihydroxyphenyl propane) be particularly preferred.
Diphenol can use individually or with arbitrary mixture.Diphenol is by known maybe can being obtained by the method known by document of document.
The chain terminator being applicable to manufacture thermoplastic aromatic polycarbonate is such as, phenol, para-chlorophenol, p-tert-butylphenol or 2, 4, 6-tribromophenol, and long chain alkylphenol, as 4-[2-(2, 4, 4-tri-methyl-amyl)] phenol, according to the 4-(1 of DE-A2842005, 3-tetramethyl butyl)] phenol or there is monoalkyl phenol or the dialkyl phenol of 8 to 20 carbon atoms altogether in alkyl substituent, as 3, 5-bis--tert.-butyl phenol, to isooctyl phenol, to tert-octyl phenol, to dodecyl phenol and 2-(3, 5-dimethyl heptyl) phenol and 4-(3, 5-dimethyl heptyl) phenol.The amount of chain terminator be generally total moles meter 0.5mol% to 10mol% based on diphenol used separately.
This thermoplastic aromatic polycarbonate has 10,000 to 200,000g/mol, and preferably 15,000 to 80,000g/mol, particularly preferably 24, the weight-average molecular weight (Mw is recorded by GPC (using the gel permeation chromatography of polycarbonate standards)) of 000 to 32,000g/mol.
Described thermoplastic aromatic polycarbonate can branching in a known way, preferably by introduce based on diphenol total amount 0.05 to 2.0mol% used trifunctional or be greater than the compound of trifunctional, such as there are those compounds of 3 and more phenolic group group.The polycarbonate that preferred use is linear, more preferably based on those of dihydroxyphenyl propane.
Homo-polycarbonate and Copolycarbonate are all suitable.Also can use based on using diphenol total amount 1-25 % by weight, the polydiorganosiloxane with hydroxyl aryloxy end group of preferred 2.5-25 % by weight prepares the Copolycarbonate of the present invention according to component A.These are known (US3419634) and prepare by known in the literature method.Copolycarbonate containing polydiorganosiloxane is also applicable; In DE-A3334782, such as describe the preparation of the Copolycarbonate containing polydiorganosiloxane.
Except bisphenol A homopolycarbonate, preferred polycarbonate is dihydroxyphenyl propane and the diphenol being different from preferably or particularly preferably mentioning based on the maximum 15mol% of diphenol total moles meter, the particularly Copolycarbonate of 2,2-two (the bromo-4-hydroxyphenyl of 3,5-bis-) propane.
Aromatics dicarboxylic acid dihalide for the preparation of aromatic polyestercarbonates is preferably two acyl dichloros of m-phthalic acid, terephthalic acid, diphenyl ether-4,4'-dioctyl phthalate and naphthalene-2,6-dioctyl phthalate.
Ratio is the mixture of the m-phthalic acid of 1:20 to 20:1 and two acyl dichloros of terephthalic acid is particularly preferred.
In the preparation of polyestercarbonate, use carbonyl halide in addition, preferred phosgene is as difunctional acid derivative.
Except the single phenol mentioned, its chlorinated carbonates and can optionally by C 1to C 22alkyl or the chloride of acid of aromatic monocarboxylate replaced by halogen atom, and aliphatic C 2to C 22single carboxyl acyl chloride is also suitable for use as the chain terminator of preparation aromatic polyestercarbonates.
The amount of chain terminator is respectively 0.1 to 10mol%, when phenolic chain stoppers based on the mole number of diphenol, when single carboxyl acyl chloride chain terminator based on the mole number of dicarboxylic dihydrazides dichloro.
In the preparation of aromatic polyestercarbonates, one or more aromatic hydroxycarboxylic acids can also be used in addition.
This aromatic polyestercarbonates can be linear and (see DE-A2940024 and DE-A3007934) of branching in a known way, and wherein linear polyester carbonic ether is preferred.
As branching agent, the trifunctional of the amount of (based on dicarboxylic dihydrazides dichloro meter used) 0.01 to 1.0mol% or polyfunctional carboxyl acyl chloride can be used such as, trigalloyl trichlorine as equal in benzene, cyanogen urine acyl trichlorine, 3,3'-, 4,4'-benzophenone tetracarboxylic acid acyl tetrachloro, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid acyl tetrachloro or the equal four acyl tetrachloros of benzene, or based on the trifunctional of the amount of diphenol meter 0.01 to 1.0mol% used or polyfunctional phenol, as Phloroglucinol, 4,6-dimethyl-2,4,6-tri--(4-hydroxyphenyl)-hept-2-ene", 4,6-dimethyl-2,4,6-tri--(4-hydroxyphenyl) heptane, 1,3,5-tri--(4-hydroxyphenyl) benzene, 1,1,1-tri--(4-hydroxyphenyl) ethane, three-(4-hydroxyphenyl) phenylmethanes, 2,2-two [two (4-the hydroxyphenyl)-cyclohexyl of 4,4-] propane, two (the 4-hydroxyphenyl sec.-propyl) phenol of 2,4-, four-(4-hydroxyphenyl) methane, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenol of 2,6-, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl) propane, four-(4-[4-hydroxyphenyl sec.-propyl]-phenoxy group) methane, Isosorbide-5-Nitrae-bis-[4,4'-(dihydroxyl triphenyl) methyl] benzene.Phenolic branching agents can add together with diphenol; Chloride of acid branching agent can add together with acyl group dichloro.
In Celanex carbonic ether, the ratio of carbonate structural unit can change on demand.The ratio of carbonate group is preferably maximum 100mol% based on the total amount of ester group and carbonate group, particularly 80mol% at most, particularly preferably 50mol% at most.The ester moiety of this aromatic polyestercarbonates and carbonate moiety can be present in this polycondensate with block form or with statistical distribution form.
This thermoplastic aromatic polycarbonate and polyestercarbonate can use alone or use with the form of any mixture.
b component
Graftomer B comprises the graftomer such as with rubber-elastic properties, it can obtain from least two kinds of following monomer substantially: chloroprene, 1, 3-divinyl, isoprene, vinylbenzene, vinyl cyanide, ethene, propylene, vinyl-acetic ester and there is (methyl) acrylate of 1-18 carbon atom in alkoxide component, that is: as such as at " MethodenderOrganischenChemie " (Houben-Weyl), 14/1st volume, GeorgThieme-Verlag, Stuttgart1961, 393-406 page and at C.B.Bucknall, " ToughenedPlastics ", Appl.SciencePublishers, the polymkeric substance described in London1977.
Preferred polymer B is partial cross-linked and has higher than 20 % by weight, preferably higher than 40 % by weight, particularly higher than 60 % by weight gel content (measuring in toluene).
Gel content measures in a suitable solvent at 25 DEG C (M.Hoffmann, H.Kr mer, R.Kuhn, PolymeranalytikIundII, GeorgThieme-Verlag, Stuttgart1977).
Preferred graftomer B comprise form (wherein B1) at B2 by following component) on) and graftomer:
B.1) 5-95, preferred 30-80 weight part is B.1.1) and B.1.2) mixture:
B.1.1) vinylbenzene, alpha-methyl styrene, the cyclosubstituted vinylbenzene of methyl, the methacrylic acid C1-C8 alkyl ester of 50-95 weight part, particularly methyl methacrylate, the mixture of vinylformic acid C1-C8 alkyl ester, particularly methyl acrylate or these compounds, and
B.1.2) 5-50 parts by weight of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8 alkyl ester, particularly methyl methacrylate, vinylformic acid C1-C8 alkyl ester, particularly methyl acrylate, maleic anhydride, the mixture of the maleimide that C1-C4 alkyl-or phenyl-N-replace or these compounds
B.2) 5-95, preferred 20-70 weight part is containing the grafting skeleton of rubber.
Described grafting skeleton preferably has the second-order transition temperature lower than-10 DEG C.
Particularly preferably be the grafting skeleton based on polybutadiene rubber.
Preferred graftomer B is such as with vinylbenzene and/or propylene is fine and/or the polyhutadiene of (methyl) alkyl acrylate grafting, butadiene/styrene copolymers and acrylic elastomer; Namely the multipolymer of type is described in DE-OS1694173 (=US-PS3564077); The polyhutadiene of, vinylbenzene fine with alkyl acrylate or alkyl methacrylate, vinyl-acetic ester, propylene and/or ring-alkylated styrenes grafting, Butadiene/Styrene or the fine multipolymer of divinyl/propylene, polyisobutene or polyisoprene, as described in DEOS2348377 (=USPS3919353).
Particularly preferred graftomer B be by following component I and II(I on II) graft reaction obtain graftomer:
I. based on graft product meter 10-70, preferred 15-50, particularly at least one (methyl) acrylate of 20-40 % by weight, or a kind of mixture of 10-70, preferred 15-50, particularly 20-40 % by weight, described mixture is based on described mixture meter 10-50, the vinyl cyanide of preferred 20-35 % by weight or (methyl) acrylate and based on described mixture meter 50-90, the vinylbenzene of preferred 65-80 % by weight
II. based on described graft product meter 30-90, preferred 40-85, the butadiene polymer of 50-80 % by weight is as grafting skeleton especially, and described butadiene polymer contains the butadiene based on component I I meter at least 50 % by weight.
The gel content of described grafting skeleton II is preferably at least 70 % by weight (measuring in toluene), and graft(ing) degree G is 0.15-0.55, and the median size d of graftomer B 50for 0.05-2, preferred 0.1-0.6 μm.
(methyl) acrylate I is the ester that acrylic or methacrylic acid is formed with the monohydroxy-alcohol with 1-18 carbon atom.Particularly preferably methyl methacrylate, β-dimethyl-aminoethylmethacrylate and propyl methacrylate.
Except butadiene, described grafting skeleton II can also count the group of the highest other ethylenically unsaturated monomer of 50 % by weight containing based on II, and such as vinylbenzene, propylene be fine, acrylate or methacrylic ester (such as methyl acrylate, ethyl propenoate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate), vinyl ester and/or the vinyl ether at alkoxide component with 1-4 carbon atom.Preferred grafting skeleton II is pure polyhutadiene.
Since it is known grafted monomer is not inevitable being grafted to completely on described grafting skeleton in process of grafting, so graftomer B according to the present invention also should be understood to refer to be polymerized by grafted monomer these products obtained under described grafting skeleton exists.
Graft(ing) degree G refers to the grafted monomer of grafting and the weight ratio of described grafting skeleton, is without unit.
Median size d 50the diameter being on it and respectively have the particle of 50 % by weight to exist under it.It can carry out measuring (W.Scholtan, H.Lange, Kolloid, Z.undZ.Polymere250 (1972), 782-796) by means of ultracentrifugation separating and measuring.
Second-order transition temperature measures according to standard DINEN61006 by means of dynamic differential thermal analysis (DSC) under 10K/min heating rate, and wherein Tg is defined as neutral temperature (tangent method).
Other preferred graftomer B such as also has by the following graftomer formed:
(a) based on B meter, the acrylic elastomer of 20-90 % by weight as grafting skeleton, and
B (), based on B meter, the polymerisable ethylenically unsaturated monomer of at least one of 10-80 % by weight is as grafted monomer, and the second-order transition temperature had at the homopolymer not having to obtain a) or multipolymer of described monomer is higher than 25 DEG C.
The second-order transition temperature that the grafting skeleton of acrylic elastomer preferably has lower than-20 DEG C, preferably lower than-30 DEG C.
The acrylic elastomer (a) of polymer B is preferably the polymkeric substance of alkyl acrylate, optionally containing other the polymerisable ethylenically unsaturated monomer based on (a) meter the highest 40 % by weight.Preferred polymerizable acrylic ester comprises its C 1-C 8-alkyl ester, such as methyl esters, ethyl ester, positive butyl ester, n-octyl and 2-ethylhexyl, and the mixture of these monomers.
In order to crosslinked, the monomer copolymerization with more than one polymerizable double bond can be made.The preferred example of cross-linking monomer be have 3-8 carbon atom unsaturated monocarboxylic acid and there is the unsaturated monohydroxy-alcohol of 3-12 carbon atom or there is the ester of saturated polyol of 2-4 OH group and 2-20 carbon atom, such as Ethylene glycol dimethacrylate, allyl methacrylate; Multiple unsaturated heterocyclic compound, such as cyanuric acid trivinyl ester and triallyl ester; Polyfunctional vinyl compound, such as two-and trivinylbenzene; But also can be tricresyl phosphate allyl ester and diallyl phthalate.
Preferred cross-linking monomer is allyl methacrylate, Ethylene glycol dimethacrylate, diallyl phthalate and the heterogeneous ring compound containing at least 3 ethylenically unsaturated groups.
Particularly preferred cross-linking monomer is cyclic monomer: cyanuric acid triallyl ester, tricarbimide triallyl ester, cyanuric acid trivinyl ester, triacryl six hydrogen-s-triazine and triallyl benzene.
The amount of cross-linking monomer is based on grafting skeleton (a) meter preferably 0.02-5, especially 0.05-2 % by weight.
When having the ring-type cross-linking monomer of at least three ethylenically unsaturated groups, this amount is restricted to be less than 1 % by weight of grafting skeleton (a) be favourable.
Preferred " other " polymerizable ethylenically unsaturated monomer for the preparation of grafting skeleton (a) can be optionally used to be such as vinyl cyanide, vinylbenzene, alpha-methyl styrene, acrylamide, vinyl-C1-C6-alkyl oxide, methyl methacrylate and divinyl together with acrylate.Preferred acrylate rubber as grafting skeleton (a) is the emulsion polymer of the gel content with at least 60 % by weight.
Other suitable grafting skeleton has grafting binding site and gel content is the silicone rubber of at least 40% (measuring in dimethyl formamide), as described in open text DE3704657, DE3704655, DE3631540 and DE3631539.
component C
Component C comprises one or more thermoplastic ethylene's base (being total to) polymkeric substance.
Suitable vinyl (being total to) polymkeric substance is that at least one is selected from vinyl-arene, vinyl cyanide (unsaturated nitrile), (methyl) vinylformic acid (C 1to C 8) polymkeric substance of monomer of alkyl ester, unsaturated carboxylic acid and olefinically unsaturated carboxylic acid derivatives (as acid anhydrides and imide).Specially suitable is following (being total to) polymkeric substance:
C.1.150 to 99, the preferably vinyl-arene of 60 to 80 weight parts and/or cyclosubstituted vinyl-arene, as vinylbenzene, alpha-methyl styrene, p-methylstyrene, to chloro-styrene), and/or (methyl) vinylformic acid (C 1-C 8) alkyl ester, as methyl methacrylate, β-dimethyl-aminoethylmethacrylate), and
C.1.21 to 50, the preferably vinyl cyanide (unsaturated nitrile) of 20 to 40 weight parts, as vinyl cyanide and methacrylonitrile, and/or (methyl) vinylformic acid (C 1-C 8) alkyl ester, as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and/or unsaturated carboxylic acid, as toxilic acid, and/or the derivative of unsaturated carboxylic acid, as acid anhydrides and imide, such as maleic anhydride and N-phenylmaleimide.
Described vinyl (being total to) polymkeric substance is resinous thermoplastic and does not contain rubber.Described multipolymer particularly preferably by C.1.1 vinylbenzene and C.1.2 vinyl cyanide obtain.
Known according to (being total to) polymkeric substance of C and can by radical polymerization, particularly by emulsion, suspension, solution or mass polymerization preparation.Preferably should have 15,000 to 200,000g/mol by (being total to) polymkeric substance, particularly preferably the weight-average molecular weight Mw (weight average is measured by scattering of light or sedimentation) of 100,000 to 150,000g/mol.
In an especially preferred embodiment, C is the multipolymer with the weight-average molecular weight Mw of 130,000g/mol of 77 % by weight vinylbenzene and 23 % by weight vinyl cyanide.
component D
Phosphonium flame retardant D be preferably selected from monomer in the present invention with oligomeric phosphoric acid ester and phosphonic acid ester, phosphonic acid ester amine and phosphonitrile, the mixture of the several components a kind of or not of the same race be selected from these groups also can be used as fire retardant.The phosphorus compound of other halogen specifically do not mentioned in this article also can use alone or uses with arbitrary combination with the phosphorus compound of other halogen.
Preferred monomer and oligomeric phosphoric acid ester or phosphonic acid ester are the phosphorus compounds of logical formula V:
Wherein
R 1, R 2, R 3and R 4represent the C1-C8 alkyl of optional halogenation, C5-C6 cycloalkyl, C6-C20 aryl or C7-C12 aralkyl separately independently of each other respectively, described cycloalkyl, aryl or aralkyl are respectively optionally by alkyl, preferably C1-C4 alkyl, and/or halogen, preferred chlorine, bromine replace
N is 0 or 1 independently of each other,
Q is 0-30, and
X refers to the monocycle or polycyclic aromatic group with 6 to 30 C atoms or the aliphatic group with the linear of 2 to 30 C atoms or branching, and they can be replaced by OH and can contain maximum 8 ehter bonds.
R 1, R 2, R 3and R 4preferably refer to C1-C4 alkyl, phenyl, naphthyl or phenyl C1-C4 alkyl independently of each other.Aromatic group R 1, R 2, R 3and R 4itself can use halogen and/or alkyl, and preferred chlorine, bromine and/or C1-C4 alkyl replace.Particularly preferred aryl is tolyl, phenyl, xylyl, propyl group phenyl or butyl phenyl and their corresponding bromination and chlorinated derivatives.
In formula (V), X preferably represents the monocycle or polycyclic aromatic group with 6-30 carbon atom.This preferably derives from the diphenol of formula (I).
In formula (V), n can be 0 or 1 independently of each other; N preferably equals 1.
Q represents 0-30, preferred 0-20, particularly preferably the integer of 0-10, and represents 0.8-5.0 in the case of mixtures, preferred 1.0-3.0, more preferably the mean value of 1.05-2.00 and particularly preferably 1.08-1.60.
X particularly preferably represents
Or their chlorination or brominated derivative, and especially X derived from Resorcinol, quinhydrones, dihydroxyphenyl propane or phenylbenzene phenol.Particularly preferably, X is derived from dihydroxyphenyl propane.
Phosphorus compound particularly tributyl phosphate, triphenylphosphate, Tritolyl Phosphate, diphenyl phosphate tolyl ester, diphenyl phosphate monooctyl ester, diphenyl phosphate-2-ethyltoluene base ester, tricresyl phosphate-(isopropyl phenyl) ester, the low polyphosphate of Resorcinol bridging and the low polyphosphate of dihydroxyphenyl propane bridging of formula (V).Particularly preferably use the low polyphosphate of the formula (V) derived from dihydroxyphenyl propane.
Most preferably according to the dihydroxyphenyl propane base low polyphosphate of formula (Va) as component D.
Known (see such as EP-A0363608 according to the phosphorus compound of component D; EPA0640655) maybe can be prepared (see UllmannsEnzyklop diedertechnischenChemie in a similar fashion by known method; 18th volume; 301st page and with nextpage, 1979; Houben-Weyl, MethodenderorganischenChemie, the 12/1st volume, the 43rd page; Beilstein the 6th volume, the 177th page).
As component D of the present invention, the mixture of the phosphoric acid ester that there is different chemical structures and/or there is identical chemical structure and different molecular weight also can be used.
The mixture of preferred use same structure and different chain length, the q value of giving is average q value.Mean value q by measuring the composition (molecular weight distribution) of phosphorus compound by high pressure lipuid chromatography (HPLC) (HPLC) and being measured by the mean value of its calculating q in 40 DEG C of mixtures at vinyl cyanide and water (50:50).
In addition, as described in WO00/00541 and WO01/18105, phosphonic acid ester amine and phosphonitrile can be used as fire retardant.
Fire retardant can use alone or use with mutual any mixture or with the mixture of other fire retardant.
If composition of the present invention has been endowed flame retardant resistance, preferably also comprise anti-dripping agent, preferably polytetrafluoroethylene (PTFE).
component E
Component E is that described acid anhydrides is unsaturated carboxylic acid anhydrides not containing the anhydride modified a-alkene terpolymer of rubber in the present invention.
Described acid anhydrides is preferably selected from maleic anhydride, Tetra hydro Phthalic anhydride, fumaric acid anhydride and itaconic anhydride and their mixture.
Described acid anhydrides is particularly preferably maleic anhydride.
Described alpha-olefin terpolymer preferably comprises the structural unit being selected from lower group: ethene, 1-propylene, 1-butylene, 1-iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hendecene, 1-laurylene, 1-tridecylene, 1-tetradecylene, 1-octadecylene, 1-19 alkene and their mixture.
Described terpolymer particularly preferably comprises ethene, 1-propylene and 1-octene as structural unit.
The described anhydride modified terpolymer not containing rubber is characterised in that described composition comprises
E1) 90.0-98.0 % by weight, preferred 92.0-97.5 % by weight, particularly preferably 94.0-97.0 % by weight terpolymer and
E2) 2.0-10.0 % by weight, preferred 2.5-8.0 % by weight acid anhydrides of particularly preferably 3.0-6.0 % by weight.
The described molecular weight Mw preferably do not had containing the anhydride modified terpolymer of rubber is 2000 – 10000g/mol, preferably 2500 – 8000g/mol, being particularly preferably 3000 – 6000g/mol, is standard test as solvent with polystyrene at trichlorobenzene by GPC (gel permeation chromatography).
The hydrocarbon fraction E1 of described anhydride modified terpolymer) preferred feature is:
Described ethylene content is 96.0-80.0 % by weight, is more preferably 92.0-84.0 % by weight;
Described propylene content is 2.0-10.0 % by weight, is more preferably 4.0-8.0 % by weight; With
Described octene content is 2.0-10.0 % by weight, is more preferably 4.0-8.0 % by weight.
component F)
Component F comprises the filler of enhancing and non-reinforcing.The example of fortifying fibre has granulated glass sphere, mica, silicate, quartz, talcum powder, titanium dioxide, wollastonite and BET surface-area at least 50m 2the pyrolytic silicon dioxide of/g (according to DIN66131/2) or precipitated silica.
Above-mentioned silica filler can be had wetting ability or can be hydrophobic by known method.In this regard such as can with reference to the open text DE3839900A1 of Germany, wherein relevant therewith disclosure forms a application's part.
The example of Non-reinforcing fillers has silica powder, diatomite, Calucium Silicate powder, zirconium silicate, zeolite, metal oxide powder, as aluminum oxide, titanium oxide, ferric oxide or zinc oxide, barium silicate, barium sulfate, calcium carbonate, gypsum and polytetrafluorethylepowder powder.
In addition, fibre fractionation can be used if glass fibre and synthon are as reinforcing filler.The BET surface-area of these fillers is preferably less than 50m 2/ g (according to DIN66131/2).
Preferred filler and strongthener are talcum, glass fibre, silicate, quartz, titanium dioxide and wollastonite.
Particularly preferably talcum is as filler.
In an optional embodiment, the inorganic powder that granularity is superfine can be used, described powder is preferably by periodic table of elements 1-5 main group or 1-8 subgroup, preferred 2-5 main group or 4-8 subgroup, the particularly preferably at least one polar compound composition of one or more metals of 3-5 main group or 4-8 subgroup, wherein at least one element is selected from oxygen, hydrogen, sulphur, phosphorus, boron, carbon, nitrogen or silicon.
Preferred compound is such as oxide compound, oxyhydroxide, hydrous oxide, vitriol, sulphite, sulfide, carbonate, carbide, nitrate, nitrite, nitride, borate, silicate, phosphoric acid salt, hydride, phosphite or phosphonate.
The superfine inorganic powder of granularity preferably by oxide compound, phosphoric acid salt, oxyhydroxide, preferred TiO 2, SiO 2, SnO 2, ZnO, ZnS, boehmite, ZrO 2, Al 2o 3, aluminum phosphate, ferric oxide and TiN, WC, AlO (OH), Sb 2o 3, ferric oxide, NaSO 4, vanadium oxide, zinc borate, silicate as Al silicate, Mg silicate, one-, two-and three-Wei silicate composition.Also can use the compound of mixture and doping.
In addition, these nano-scale particles can carry out surface modification to realize and the better consistency of described polymkeric substance with organic molecule.Like this, hydrophobicity or hydrophilic surface can be produced.
Particularly preferably be the aluminum oxide containing hydrate, such as boehmite or TiO 2.
The median size of described nano particle is less than or equal to 200nm, is preferably less than or equal to 150nm, particularly 1-100nm.
Granularity and particle diameter all refer to median size d 50, according to people such as W.Scholtan, Kolloid-Z.undZ.Polymere250 (1972), 782-796 page is measured by ultracentrifugation separating and measuring method.
Described mineral compound can exist as powder, thickener, colloidal sol, dispersion or suspension.Powder can by being obtained by dispersion, colloidal sol or suspension sedimentation.
Described powder can be introduced in this thermoplastic composition by ordinary method, such as, pass through the inorganic powder that directly kneading or extrusion molding composition and granularity are superfine.Preferred method prepares master batch, such as at least one component of flame-retardant additive and the moulding compound according to the present invention in monomer or solvent, or the co-precipitation of thermoplastic component and the superfine inorganic powder of granularity, such as by aqueous emulsion and the superfine inorganic powder co-precipitation of granularity, be optionally the dispersion of the superfine inorganic materials of granularity, suspension, thickener or solation.
Component G (other additive)
Said composition also can comprise other conventional polymer additive, as retardant synergist, anti-dripping agent (such as the compound of fluorinated polyolefin, silicone and Kevlar class material), lubricant and releasing agent (such as pentaerythritol tetrastearate), nucleator, stablizer, static inhibitor (such as graphitized carbon black, carbon fiber, carbon nanotube and organic antistatic agents, as polyalkylene ether, alkyl sulfonic ester or the polymkeric substance containing polymeric amide) and dyestuff and pigment.
As anti-dripping agent, particularly as powder or as such as using tetrafluoroethylene (PTFE) with the mixture of the condensation of B component or containing the composition of (PTFE), such as PTFE with containing methacrylic acid styrene esters or containing the polymkeric substance of methyl methacrylate or the master batch of multipolymer.
Fluorinated polyolefin as anti-dripping agent is high molecular and has higher than-30 DEG C, and usually above the second-order transition temperature of 100 DEG C, the Oil repellent had is preferably 65-76, especially 70-76 % by weight, the median size d had 50for 0.05-1000, preferably 0.08-20 μm.Usually, the density of described fluorinated polyolefin is 1.2-2.3g/cm 3.Preferred fluorinated polyolefin is tetrafluoroethylene, poly(vinylidene fluoride), tetrafluoroethylene/hexafluoropropylene and Tefzel.Fluorinated polyolefin be known (see " VinylandRelatedPolymers " of Schildknecht, JohnWiley & Sons, Inc., NewYork, 1962,484-494 page; " Fluorpolymers " of Wall, Wiley-Interscience, JohnWiley & Sons, Inc., NewYork, volume13,1970,623-654 page; " ModernPlasticsEncyclopedia ", 1970-1971, volume47, No.10A, October1970, McGraw-Hill, Inc., NewYork, the 134th and 774 pages; " ModernPlasticsEncyclopedia ", 1975-1976, October1975, volume52, No.10A, McGraw-Hill, Inc., NewYork, the 27th, 28 and 472 pages and USPS3671487,3723373 and 3838092).
They can be prepared by known method, and such as, by tetrafluoroethylene catalyzer with formation free radical in water-bearing media, such as Sodium persulfate, Potassium Persulfate or ammonium peroxydisulfate are at 7-71kg/cm 2with 0-200 DEG C under pressure, preferably at 20-100 DEG C of temperature, be polymerized (further details are for example, see US patent 2393967).According to its type of service, the density of these materials can be 1.2-2.3g/cm 3, and median size can be 0.05 and 1000 μm.
Be 0.05-20 μm, preferably 0.08-10 μm according to the median size that the preferred fluorinated polyolefin of the present invention has, and density is 1.2-1.9g/cm 3.
The suitable fluorinated polyolefin that can use in powder form be have median size for 100-1000 μm and density be 2.0g/cm 3-2.3g/cm 3tetrafluoro ethylene polymer.Suitable tetrafluoroethylene polymer powder is that the product that is obtained commercially and such as DuPont sell with trade(brand)name Teflon.
As the stablizer according to component G, preferably use sterically hindered phenol and phosphite or their mixture, such as Irganox B900 (BASF).Pentaerythritol tetrastearate is preferably used as releasing agent.
According to moulding compound of the present invention, comprise component A-F and optionally other known additive G, such as stablizer, dyestuff, pigment, lubricant and releasing agent, nucleator and static inhibitor, by mixing each composition in known manner and carrying out melting mixture or melt extrude preparing at the temperature of 200oC-330oC in conventional equipment such as inner kneader, forcing machine and twin screw extruder.
Therefore present invention also offers the method that preparation comprises component A-F and the optionally thermoplastic composition of additive G, described composition carries out melting mixture upon mixing or melt extrudes at the temperature of 200-330oC in conventional equipment.
The mixing of each composition can in known manner continuously or side by side in about 20 DEG C (room temperatures) or carry out at higher temperatures.
Moulding compound of the present invention may be used for preparing various types of moulded work.Especially, moulded work can be prepared by injection moulding.The example of the moulded work that can prepare has: various types of casing component, such as household electrical appliance as televisor and HiFi equipment, coffee machine, mixing machine, office equipment is as indicating meter or printer, or the wrapper plate of building field and the parts of automotive field.Also electric works field is used in, because they have good electrical property.
Described moulding compound is particularly suitable for the thin-walled casing component prepared in Electrical and Electronic field.
Other form processing prepares moulded work by blowing or deep-draw by the sheet material made before or film.
the preparation of moulding compound and test
Use twin screw extruder (ZSK-25) (WernerandPfleiderer), material listed in table 1 and table 2 is carried out mixture and granulation with the throughput of the rotating speed of 225rpm and 20kg/h under the machine temperature of 260 DEG C.Described finished product pill is processed to form corresponding sample (temperature of charge 240 DEG C, die temperature 80 DEG C, flow front speed 240mm/s) on injection moulding machine.
Use the performance of method characterizing sample below:
Mobility measures according to ISO11443 (melt viscosity).
Notched Izod impact strength ak according to ISO180/1A be of a size of 80x10x4mm one-sided injection (einseitigangespritzt) breach sample on measure.
Shock strength ak measures on the unnotched sample of one-sided injection being of a size of 80x10x4mm according to ISO180/1U.
Melt flowability (MVR) melt volume-flow rate (MVR) measured at 240 DEG C of temperature and 5kg load according to ISO1133 is evaluated.
Burning behavior is measured on the sample being of a size of 127x12.7x1.5mm according to UL94V.
ESC behavior is measured under the outer layer fiber strain of 2.4% according to ISO4599 (environmental stress cracking (ESC) test) in EnergolHLP-150 hydraulic efficiency oil or in toluene/isopropanol 60:40.
The following example is used for explaining the present invention further.
Embodiment
component A1
Based on the linear polycarbonate of dihydroxyphenyl propane, the weight-average molecular weight-M had wfor 27500g/mol (measured in methylene dichloride by GPC, polycarbonate is as standard).
component A-2
Based on the linear polycarbonate of dihydroxyphenyl propane, the weight-average molecular weight had is-M w20000g/mol (measured in methylene dichloride by GPC, polycarbonate is as standard).
b component-1
There is the ABS graft polymer of nucleocapsid structure, by the mixture formed by 33 % by weight vinyl cyanide and 67 % by weight vinylbenzene based on abs polymer meter 50 % by weight at the particulate state crosslinked polybutadiene-styrenerubber (styrene content of described rubber: 10%) (median size d based on abs polymer meter 50 % by weight 50=0.32 μm) there is emulsion polymerisation preparation.
b component-2
There is the ABS graft polymer of nucleocapsid structure, by the mixture formed by 27 % by weight vinyl cyanide and 73 % by weight vinylbenzene based on abs polymer meter 43 % by weight at particulate state crosslinked polybutadiene rubber (the median size d based on abs polymer meter 57 % by weight 50=0.35 μm) there is emulsion polymerisation preparation.
B component-3
Abs polymer, by the mass polymerization preparation under the Polybutadiene-styrene block copolymer rubber of the styrene content 26 % by weight based on abs polymer meter 18 % by weight exists of the mixture formed by 24 % by weight vinyl cyanide and 76 % by weight vinylbenzene based on abs polymer meter 82 % by weight.Weight-average molecular weight-the M of san copolymer part free in abs polymer wfor 80000g/mol (being measured in THF by GPC).The gel content of described abs polymer is 24 % by weight (measuring in acetone).
Component C
The multipolymer of 77 % by weight vinylbenzene and 23 % by weight vinyl cyanide, weight-average molecular weight-M wfor 130000g/mol (being measured by GPC), prepared by substance law (Masseverfahren).
component D
The low polyphosphate of dihydroxyphenyl propane base
。
Component E
Ethylene-propylene-octene-copolymer-maleic anhydride (ethene: propylene: octene 87:6:7), CAS .31069-12-2, molecular weight-M w5000g/mol, density 940kg/m3, acid number 60mgKOH/g, maleic anhydride content is 4.4% based on described multipolymer E.
Component F
HTPUltra5C, talcum, from ImifabiS.p.A, wherein content of MgO is 31 % by weight, SiO 2content is 61.5 % by weight and Al 2o 3content is 0.4 % by weight.Particle diameter d 50it is 1.3 μm.
Component G-1
The mixture (CycolacINP449 from Sabic) of the condensation of the copolymer emulsion of fluorinated polyallyl hydrocarbon emulsion and styrene-based-vinyl cyanide.
Component G-1a
CFP6000N, polytetrafluorethylepowder powder (manufacturers: DuPont, Geneva, Switzerland).
Component G-2
As the pentaerythritol tetrastearate of lubricants/release agents.
Component G-3
Phosphite ester stabilizer, the Irganox B900 (mixture of 80%Irgafos 168 and 20%Irganox 1076; BASFAG; Ludwigshafen/Irgafos 168 (three (2,4-, bis--tert-butyl-phenyl) phosphorous acid ester)/Irganox 1076 (2,6-, bis--tertiary butyl-4-(octadecane oxygen base carbonylethyl) phenol).
Table 1: the composition and performance of moulding compound
As can be seen from Table 1: the composition with the embodiment 2 and 3 of the ethylene-propylene-copolymer-maleic anhydride of 1%-2% achieves object of the present invention, that is: good under 1.5mm and UL94V-0 grade (breach) shock strength, mobility and chemical-resistant combine.
Table 2: the composition and performance of moulding compound
As can be seen from Table 2: the composition with the embodiment 6-8 of the ethylene-propylene-copolymer-maleic anhydride of 1%-2% achieves object of the present invention, that is: good under 1.5mm and UL94V-1 or V-2 grade (breach) shock strength, mobility and chemical-resistant combine.

Claims (14)

1. fire-retardant thermoplastic composition, it comprises
A) at least one aromatic polycarbonate of 50.0-90.0 weight part,
B) at least one graftomer of 4.0-14.0 weight part,
C) at least one vinyl (being total to) polymkeric substance of 0.0-15.0 weight part,
D) at least one phosphonium flame retardant of 1.0-20.0 weight part,
E) at least one of 0.5-5.0 weight part is not containing the anhydride modified alpha-olefin terpolymer of rubber,
F) at least one filler of 0.0-25.0 weight part,
G) other conventional additives of 0.0 – 10.0 weight part,
Wherein component A)-F) weight part sum add up to 100 weight parts,
It is characterized in that, the described anhydride modified ter-polymers not containing rubber has the molecular weight Mw of 2000-10000g/mol.
2. moulding compound according to claim 1, is characterized in that: contained component E) ratio be 1.0-2.0 weight part.
3. according to the moulding compound of claim 1 or 2, it is characterized in that: contained component F) ratio be 12.0-18.0 weight part.
4. according to the moulding compound of claim 1 or 2, it is characterized in that: contained component G) ratio be 0.5-2.0 weight part.
5. moulding compound according to claim 1, is characterized in that: described acid anhydrides is selected from maleic anhydride, Tetra hydro Phthalic anhydride, fumaric acid anhydride and itaconic anhydride and their mixture.
6. moulding compound according to claim 5, is characterized in that: described acid anhydrides is maleic anhydride.
7. according to the moulding compound of claim 5 or 6, it is characterized in that: alpha-olefin terpolymer comprises the structural unit being selected from lower group: ethene, 1-propylene, 1-butylene, 1-iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hendecene, 1-laurylene, 1-tridecylene, 1-tetradecylene, 1-octadecylene, 1-19 alkene and their mixture.
8. moulding compound according to claim 5, is characterized in that: the described anhydride modified terpolymer not containing rubber comprises
E1) 90.0-98.0 % by weight terpolymer and
E2) acid anhydrides of 2.0-10.0 % by weight.
9. according to the moulding compound of claim 1 or 2, it is characterized in that: described terpolymer is made up of ethene, 1-propylene and 1-octene structural unit.
10. moulding compound according to claim 8, is characterized in that: the hydrocarbon fraction E1 of described anhydride modified terpolymer) feature be
Ethylene content is 96.0-80.0 % by weight;
Propylene content is 2.0-10.0 % by weight; With
Octene content is 2.0-10.0 % by weight.
11., according to the moulding compound of claim 1 or 2, is characterized in that: use talcum as filler F).
12. moulding compounds according to claim 1, is characterized in that: described phosphonium flame retardant (D) is the fire retardant of logical formula V
Wherein: R 1, R 2, R 3and R 4represent the C of optional halogenation separately independently of each other respectively 1-C 8alkyl, C 5-C 6cycloalkyl, C 6-C 20aryl or C 7-C 12aralkyl, described cycloalkyl, aryl or aralkyl are distinguished optionally by alkyl and/or halogen substiuted,
N is 0 or 1 independently of each other,
Q is 0.80-5.00, and
X refers to the monocycle or polycyclic aromatic group with 6 to 30 C atoms or the aliphatic group with the linear of 2 to 30 C atoms or branching, and they can be replaced by OH and can contain maximum 8 ehter bonds.
13. moulding compounds according to claim 1 are for the preparation of the purposes of moulded work.
14. moulded works prepared by moulding compound according to claim 1.
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TW201329158A (en) 2013-07-16
MX2014003605A (en) 2014-04-25
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US8822576B2 (en) 2014-09-02
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WO2013045544A1 (en) 2013-04-04
CA2849955A1 (en) 2013-04-04

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